Dipyridinium compound



UNITED, STATES r This invention relates pound or product, and to the manufacture of indicated by:

Patented Nov. 20, 1951 PATENT OFFICEIYF.

as'zao oz DIPYRJDINIUM COMPOUND Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd. poration of Delaware No Drawing. Original Wilmington, DeL, a corapplication April 2, 1945,

Serial No; 586,265. Divided and this application November 26, 1945, Serial No. 630,972 r to a new chemical comsame, our present application being a division of our pending application Serial No. 586,265, filed April 2, 1945, now Patent No. 2,429,999.

5 One object of our invention is to provide a new -material or composition of matter, that is particularly adapted for use as a demulsifier in the resolution of crude oilemulsions, but which is also capable of use for various other purposes, or

in various other arts. i Another object of our invention is to provide a practicable method for manufacturing or pro- I l ducing the new material or composition of matter abovereferred to.

The new material or composition of matter herein described, consists of a diquaternary compound, particularly a dipyridinium compound of adimerized polyene fatty acid containing two amido radicals, and the pyridinium radicals are linked with the acyl radical of the dimerized acids in the manner hereinafter described.

The following will describe one simple aspect of the present invention and will serve to illustrate the type of compound contemplated. If the dimerized fatty acid hereinafter described is HOOC-RCOOH then such product can be converted into a hydroxylated diamide by reaction with two moles of. monoethanolamine, or two moles of diethano'l'a'mine,or' by reaction with ammonia and subsequent oxyethylation to yield a compound of the following composition;

CiHlOH Such compound can then be reacted with one ortwo moles of a pyridinehydrohalide, for instance, pyridine hydrochloride, so as to yield a compound of the-following composition:

1 Claim. (01; 260-295) Such dipyridinium compound of the quaternary type exemplifies one example of the type of compound herein contemplated.

The dicarboxy acids herein contemplated as reactants, or their equivalent, such as their ethyl or methyl esters, are obtained by the polymerization, and principally, the dimerization of esters of unsaturated fatty acids, particularly conjugated diethylenic acids. Such dimerized acids or their esters are well known compositions and have been used for various purposes, such as the manufacture of a resinous or synthetic coating material obtained by reaction between such dimerized compounds and certain diamines. (See Oil and Soap, volume 21, No. 4, age 101..)

The chemistry of polymerization has been discussedin the literature, but for convenience, reference is made to U. S. Patent No. 2,347,562, dated April 25, 1944, to Johnston, where the folo lowing appears:

2 moles methyl ester 9,11-octadecadienic g5 acid (originally present and/or formed by isomerization of 9,12, isomer) (OHahF-OOH:

H H HIO EO-C=C(GH:)1COCHa 30 m 11 -(CH);CH|

As to the preparation of such polymerized acids or esters, it is to be noted that any polyene fatty acid or its ester may be employed. as a raw material. In fact, one may use a mixture, such as one which occurs naturally in various drying oils. The most important of these are the octadecadienic or octadecatrienic fatty acids or their esters, but the polymeric fatty acids containing 20, 22 and 24 carbon atoms found in fishoils are also suitable.

Examples of the polyene fatty acids, the esters of which are polymerized, are the following: 9,11- and/or 9/12-0ctadecadienic acids, (obtai n able from perilla oil, linseed oil and other drying oils) both ,alphaand beta-eleostearic acids (obtainable from tung oil), etc.

If esters of the polyene fatty acids be ernployed, such esters may be producedby direct esterification of the fatty acids withthe, alcohol which has been selected, but it is generally more economical and more convenient to produce the meric state, even' though some polymershigher than the dimeric state may'beif produced, for. instance, trimers ortetramersI If-?.1desired; such polymers can be separated "from each other; -inso-- far that the dimers can be separated from the higher polymers, such as the trirners or tetramers. The method employedinvolvesgselective solvent action, but does not require'iful'therf-de-Q scription, for the reason that there is no objection to the moderate presence of mgherpmymers along with the dimers' herein contemplated for Yi'itidnf and *if polymerization is -conducted under comparatively mildconditions 'so as to polymerize not over 50'% of the polyene-acid ters,-then and in thatevent, the product obeamed "is '-*pr'incipally the dimeric product.- In

about one-half an hour to about o'hou'rs'is siiit-- able, and in most instances, the polymerization may be'efiectedinnotover '12"ho'u'rs. -Dimeri'zation can usuallybe accomplished in one-half this period ofitime. 1f a conjugated-unsaturated ester, such as the methyl 'ester -bf eleo'stearic acid be employed,.a suifi'cient' degree ofpolyrnerization may be obtained within'one-half to one hour at about 300 C., whereas, the methyl linolenates i-tandlinoleatef'gnerallyrequire from about to 12 hours or more. To speed up the polymerization process,'sliitable'catalysts may be added, examples of which are 'fullers earth (preferably acid-treated), bentonite (preferably acid-treated), stannic chloride, "etc. If catalysts be employed, it is sometimes possible to use lower tematiires' landshdrter periods of'time, or shorter ib'ds' ofitime, than thoseindicatedabove;

In generah it is preferred to conduct thegpolyeriz'a'tion in an inert atmosphere of carbon dioxideinitrog'en or, other inert gas. izationis preferably continued until the refractive ind ex', density and average *molecular-weight E ap'pro'ach' constant value. At this point, the polymerized'esters are separated from thexu'npolymerized esters by any suitable method. -In" subse'quent examples; thereis suggested the sepation of these esters by distilling off thezunp'olymerized esters at anabsolute pressure ofabout '5- mmi of mercury; and at temperatures up to The polymer about' 300 0. Another 'way in whichiithisseparation may be effected is'by' extraction with' of the product to the polymeric state, it will be found the bulk, if not all, are readily obtainable in the dimeric state.

I Previous attention has been directed to the 5 fact thatthe esters of any. polyene? higher fatty acid may be employed or mixtures thereof. Poly- ;il inerization of the kind indicated is concerned y bean' and'linseedoils. (See lndustriali iand Engineering Chemistry,'volume 34,:- page 237,- and U. -S.': Patent No. 2,350,583, :dated June 6; 1944,-to

- Bradley.) Thus; the raw materials herein-contemplated include, among others; the: isomerized fatty acids or esters obtaned from unsaturated -highler Iatty acids having at leasttwo n'on -conjugate' 'doublefbonds. Such 'materials-are-ob- =tainablei for examplefrom linssed 'oi1,-soyabean 1 oil, perilla oil; poppyseedioil, "cottonseed oiL- -sun- 3O flowerseed oil, and anumberof'fish-oi-ls. The

-' fatty acids; prior to isomerization, generally have =an iodi'ne numberof 110, orsubstantiallyahigher.

A further description of polymeric fatty acids and their compounds is found in U. S: PatentNo.

2,357,839, dated September 12, 1944, to Manley and Evans. Note that in saidfpa'tent such acid is referred to as a polyrneric fat aCid. =By'ana10- gy, the 'dimeric acid would be referred to--as dimeric' fat acidf.

,ziFromaspractical'standpoint, 'two bther facts are 'of marked interest. There is no'w available a solvent-treated dehydrated castor oilor 'fatty a'c'id i'derivativey in which the 9,11 isomer is .Zpresent to the extent of approximately 85 This commercial product 'is -particularly desirable :as

plated compounds. i-Anoth'er factor of interest is recognition .of .the effectiveness of certain catalysts ln 'co'ri verting' rion 'con jugated unsaturated *ffatty 'oilsor' ciusysc as 'td'resultin'the conju ated liso inerl Fcr'instance; see Oil andsoapyvoiume Q21, Nol'll, pageszs. w

PoLYMErrizEDf EsTEa 7 Example 1- 7' i 800 parts ofthe methyl esters of tung oil fatty acids arehe'a ted, preferably in-an atmosphere of carbon dioxide or other inert gas, to a temperature of aboutw275 C. in approximately 40 min- 9 utes and the temperature is -'maintained at this point for about one half an hour. The relatively volatile and -unpolymerized esters' are removed by Y distillation at about 1-"-5.mm-.r ofimercury absolute pressure, *the temperature --beingrgradually raised to about 300 (3., "leaving'aresidue containing 365-380 parts i of non-volatile polymerized esters.

"POLYMERIZED ESTER "Example" 2 p LUO'O'parts of the methyl estersof'the fatty acids of a solvent-treated dehydrated cast onoil, the. major portion, for instance, to of which contains the methyl ester of 9,1 1- and;9,12- 75 octadecadienic acid, are polymerized at 300 C.

a reactant for preparation of hereinacontem- No.1 '2,329,700, dated Sept'e'm 21,1943, to De .emaooa for about -3, hours (in, ,an ginert atmosphere. The 1 volatile and unpolymerized esters are removedby distillation at 1-5 mm. of mercury absolute pressure, the temperature being gradually raised to about 300 C., leaving .asa residue about 450-460 parts of non-volatile polymerized esters.

POLYMERIZED ESTER- Example 3 2,000 parts of the methyl esters of the fatty acids of soyabean oil are mixed with 200 parts of activated bentonite (Super-Filfiol) and the mixture is heated, preferably in an inert atmosphere at about 280 C. for about one-hall. hour.

The product is filtered and the volatileand unpolymerized esters are'removed by distillationflat 1-5 mm. of mercury absolute pressure, the temperature being gradually raised to about 300 0., leaving as a residue about 833-840 parts of polymerized esters.

In numerous acylation reactions, the acyl radical can be introduced bymeans of various reactants, for example, the acid itself or the ester thereof, particularly a low molal ester. Thus, if

the use of the acid results in the elimination of. 1 water as a volatile resultant, similarly .the use of to the amino nitrogen atom, i. e., in amido form,

or may be present as an ester-linked radical. In the latter event the amido radical present'must be that of a low molal carboxy acid, for instance,

one having '7 carbon atoms or less, such as acetic acid, butyric acid, etc.

The reactions of the kind referred to arewell known in connection with high molalmonocarboxy acids, in which instance they result in the formation of a mono (quaternary) compound.

1 Another procedurejdepends on the reaction of the amide with formaldehyde or paraformaldehyde, so as to yield the hydroxymetal amide. The reaction involved may beindicated in the following manner:

. I H H RCO +o=o RCON.COE 11 1111 See U. S. Patent No. 2,' 146,392, dated February '7,

1939, to Baldwin and Walker.

Another. reaction involves the formation of the ethanol ordiethanolamide, or comparable compound, as described previously. Other suitable reactants include products obtained by treating the unsubstituted amide with various oxy ethylated agents, such as ethylene oxide, propylene oxiderbutylene oxide, glycide or methylg1ycide,' or else "forming the comparable amide by "reactionwith monoor diethanolamine, monoor dipropanolamine, monoor dibutanolamine,

or with amines suchas ethyl ethanolamine, benzyl ethanolaminecyclohexyl ethanolamine, phenyl ethanolamine, "or the like. See U. S. Patent Groote and Keiser. .oi 11: 1 l

, in, is, to .be noted mat-1r the amide indicated is reactedwith a plurality of ethylene oxide or equivalent, for instance, 4 moles, then the hydroxyalkyl radicals are interrupted by an oxygen atom, which may be indicated in the'following manner:

ROON/ +4O2H40-- noon 021140 CBHAOH 11 4 CzEhOlI Suchoxygen atom interruption of the carbon atom chain does not detract from the activity of the hydroxyl group, and thus, any reference to an alkylene radical or hydroxyalkyl radical includes such radicals in which such interruption takes place. See U. S. Patent No. 2,329,702,

dated September 21, 1943, to. De Glroote and Keiser.

Other comparable derivatives are obtained from such compounds as 2-amino-l-butanol, 2-amino- Z-methyl-l-propanol, 2-amino 2 methyl- 1,3- propanediol, 2-amino 2- ethyl-1,3-propanediol and tris(hydroxymethyl)aminomethane. See U. S. Patent No. 2,329,701, dated September 21, 1943, to De Groote and Keiser.

As to the type of reactant where a lowmolal acid such as acetic acid, propionic acid, butyric acid, valeric acid, hydroxyapetic acid, lactic acid orthe like, furnishes the acyl radical which bea 1 comes part of the amido radical and in. which the high molal acyl radical, such as a higher fatty acid radical, is present in ester form, see U. S. Patent No. 2,335,262, dated November 30, 1943, to De Groote and Keiser.

It has been pointed out that the herein contemplated compounds are derivatives of certain 1 high molal dimeric acids previously indicated in their simplest form as:

HOOC-RCOOH One specific example of such acids is the following: 1 1 I J ((IJHZM Polycarboxy acids, and particularly dicarboxy acids, may be reacted in' the conventional manner with the same conventional reactants as monocarboxy'acids, ,or monocarboxy esters, so as to give dipyridinium compounds which bear a simple genetic relationship to the monopyridinium compounds previously described.

Such procedures may be illustrated in the following manner. Reaction of such dicar'boxy acids oresterswith ammonia yield the amides of the following structures:

. Such amides may be treated with 2,4,8, 8 ormore moles of. ethyleneoxide propylene oxide, hutyle'ne i thd dicarboxy r its equivalent.Erna-reaction may be ind" the follovvingiimannerz the following structures:

H O O RiO)H \Nt s ts mom} H br icam b"-"": -,.;%*mo :n "H0111 v .7 g i In the above reaction' no att'emptismade to show .IIHK R1I)/III .h thatlthe occurrenceioiRiQ may be repetitious,

. I (although-obviously; such a repetitionmay. appear, wherein R10 is the alkylene oxide radical and n asirldicatedabyn-in'the structuraliormulabflthe is a s'mall wliole number varying from 1 to 5. reactantpreviously depictedi I I a c It is to he noted -that=if .thedicarboxy acidor its I TiIihe greactantsi.previo islyedescribed-for. comequivalent is treated with paraformaldehyde in binationwithpyridine hydrochloriderortthe equivthernanner"described in the aforementioned ale'ntnnay. beqsummarizd'ilbylthe'following U-Ii-S:Patent No;'2,146;392, 1then-in-suchdnstance, Iform'ula'e: it T 7 i i i "the?radical Ridirectly= attached' to-the amido fionuemh 7 -nitro gen atom; may be a methylene 'radical, but I i i in ali-otheroccurrences, R1 represents'theethylene: No C R 0 ON -oxide radical, "the; propylene-oxide radical,=-the sv i InRiOH butylene oxideradical; the glycideradicalfi or QHQRKQRM ,(RLOMRIOH vmethwglycide' radical. a I GORCOIN I I Diamides of the kind described may, of -course, be'obtainedvby reaction with the:dicarboxyracid,,; RK OT- I 'i MR'i'OH witsester onsome other equivalent,-with= various Q (RIQ'IRIOE aaminea ssuch asvmonoethanolamine,hdiethanol- A. i j l .7 aa'mine, smonopropanolamine, ndiprjopanolamine, m F ethyl -ethano1amine, benzylethanol'amine, -:etc. 0 1( 1 I f "00121 iThe amine so obtained'. can be subjected to: oXy- .iInlithe above formu-l ae -Rg representsv a .hydroalkylation j as 'if suchc mp fi wcarbon radical containing not over 7 carbon u-derived i a ly y the action of an y atoms and derivedffor example,.-from -henzy1- --oxide. 7 r ,1 amine,"acyclohexylamine, aniline, hexy-lamine, -=Iniithe above {intermediates-it riS-n'tO'bG noted .amylaminamutylamine,or: the-like; -.-Similarly, that the high;molal acid or :its -equivalenticonmay: Jb L ,hydrogenrat m, as, l 'fi b Q-amide Iewlic Whichimust be present when amonoethanolamin e, monopropanolamine, in eaeh -instance. It has' be poi t d u monobutanolamine bra-the.like,arelemployed, or the' amid radi ala ay h -p e t in 'suchla-lform when rthe unsubstitutewdi-amide streated with 'brj structure .thesacyl radical ".Of' amido moles of, ethylene oxide 0 1 twumoles of-pro I linkage is furnished by mm--'py1ene-oxide,;0rtwo moles of'bu-tyleneoxide; The molal -carboxyi acid," such as a'ceticacid,-pr0pi0nic -;va1ue,of.,n been-, changed so 3 5.130, vary from ac d; -a t inF yc i olow molal 0 .-to-14,-- in-- orderstoi showthatatheramust always carboxy acids :having 1 7-:carbon- -atoms orzl'ess. be one livdroxt'l radical, as partof: each amide For instance, acetic acid;butyrieiacid;orithedtke, J Qdi I, nd show. that lthe (total variation-of can be PPY sultlable primary e repetitious ether linkagest'remainsthe-same. as

having an alkarrorradicalfsuch-as monoethanoL I 7 93111119, -'1 nonopr01 ah rmvnobutanolamlpe, lniorder to til-l-ustrate -the above types further, or the 1 B, 0 W y Secondary m -,rthectfollowingtexamples-areiincluded "Inf-each two Such radicals such as diethanolammei instance referenceh me-tdimeric acid-4s. inpropanolamine, etc. If"reactiori:takes place w ith a b the b im m acids Shown Pnmary amme' Fi eq m in(therdetai-ledastructurebv a previous formula. cation, suchiproductmustbereacted with an i alkylene oxide'so as to convert it into a secondary "D M Ebcdfitple'l amine having two alkanbl'rad'i'cals or the equiva s M y e mlde btamed y react "'55 One pound mole of the dimeric acid previously described by actual structural formula, is reing the acid, for example, acetic acid, or its equiv-" alent, such as ethyl acetate with ammonia, can l a i V be subjected to oxyalkylafionI 56 as to produce an acted w1th 2 pound moles of ethylethanolamme.

I I HYDROXYLATED DIAMIDE I V A Example; 2

' equivalent "reactant. suchgiprocedures aresdescribed in "the aforementioned- Ur: S, Patent-iNo.

I propanolamine is suhstituted' fonethyl- -thanolainine in the-previous example 2,335,262. In anyevent; theiresult ofilsuchfpro cedurezisito yield a reagent otithe'vstrueture O IKRiOfiH i I II ...HYDROXYILATED1DIAMIDE I 1 265 iEwampleig a a I The'tvvo amine' reactants pr'eviously described w n-which R2CQ -1S the8 .Cy 1{0211116941 Of aJOW IHOIQII 1 i I monocarboxy acid having 'Lcarbonatomsordess, J FQ'F Q T i nQ 3 are l ii ir li a 6 and R10 and n have their prior significance. M 9??? FP of ethylene oxlde i mn- Having obtained a reactant of the kind abova-rzoi em 7 V r 7 described, 2 molesaof such reactant are esterified in the customary manner withithe reactants thus a A t E z 4 Y described, following the same procedure in every m e :irespect; asidescribediimthe:aforementionedx Us. i ment Heir-2335 26Zynsingwofmoume;zzmolesziofi'flfi oxide in the previous examplav w Butylene foxidel:ismsubstitutedsrorciethylene 9 c HYonoxYrlA'rEn :oIAMrnn Earample The dimeric acidpreviously described is re-? acted with ammonia so as to produce the diamide. The one pound mole of the diamideis reacted with 2 pound moleswlv pound moles, 6 pound moles, 8 pound moles, or pound moles of ethylene oxide. Similarly, propylene oxide or butylene oxide may be substitutedforethylene are identical with those obtained by treating. the diamide with the corresponding alkylene oxide.

HYDROXYLATED DIAMIDE Example 7 2 pound moles of diethanolamine are reacted with 2 pound moles of acetic acid, or else 2 moles of acetamide are treated with 4 pound moles of ethylene oxide, so as to yield 2 pound moles of the compound of the following composition:

(RICO NC2H4OH wherein RC0 is the acyl radical. 2 pound moles of such hydroxylated amide are reacted with 1 pound mole of the dimeric acid previously.described, so as to produce a reactant of the type last mentioned-in the previous summary.

HYnRoxYrATEn DIAMIDEi j Example 8 s I In the immediately previous example, the compound of the structure l l NC2H4OH is treated with 2 or 4 moles of ethylene, propylene,

coh'olic hydroxyl groups in the amide, even if.

acetic acid or butyric acid is employed. For this reason, the reaction product obtained between such polyhydroxylated amide and the :di-

meric acid may represent apolymer which is resinous in nature, rather than the simpler monomer previously illustrated.

We desire to point out that we are aware of the,

fact that there are other reactants, which, at first glance, appear to bear a superficial relationship to the reactants herein contemplated. One might assume that such reactants could be employed to produce products comparable to those herein described. We have found the contrary to be true. For instance, we are aware that there are a variety of other high molal dicarboxy acids, such as sebacic acid, analogues of the same, etc.

Other classes include dimers of abietic acid, etc.

Acetalized ricinoleic acid. is an additional example. Diels-Alder and Clocker adducts represent another type, particularly when derived from maleic t anhydride, etc. We have not found such particuor butylene oxide prior to reaction with the dimeric acid. V

HYDROXYLATED DIAMIDE. Example 9 The same procedure is followedas in the immediately preceding Example 8, except that the butyric acid or lactic acid derivative or hydroxyacetic acidderivative, is employed instead of the acetic acid derivative.

Part of the previous examples indicate one obvious aspect of the compounds herein contemplated. If in the last example hydroxyacetic acid or lactic acid had been employed instead of the acetic acid derivatives, then the amide,

priorto reaction with a dimeric acid, would be polyfunctional insofar that it would, have at least two alcoholic hydroxyl groups as part of l'ar products could be substituted for the reactants herein described, and particularly, the dimeric acids indicated in detail.

The efiectiveness of the compounds herein described for various uses, and particularly demulsification, is undoubtedly related to the surface activity. The usual concept of surface activity, and particularly in regard to the orientation at interface of wetting agents or the like, is concerned with the balance between a hydrophobe and a hydrophile group. Such concept does not appear;

to lend itself to any particularly satisfactory ex planation of compounds of the type herein contemplated, wherein the hydrophobe group is fixed between two hydrophile groups. Naturally, such a molecular structure does not seem to be suscepti.

ble to the conventional orientation, where there is one hydrophile and one hydrophobe group in the molecule. This difierence is marked by the particular effectiveness as a demulsifier on nu merous California emulsions, in comparison with the monopyridine compounds described in various aforementioned patents.

Previous mention has been made of the fact that the second class of reactants herein employed is a hydrohalide of a member of the pyridine series. Such hydrohalides include the hydrochlorides, hydrobromides, etc. Members of the pyridine series suitable as reactants include pyridine, alkylated derivatives of pyridine, par

ticularly alkylated derivatives, in which the alkyl lines, along with c-methyl homologues thereof.

Coal tar bases represent mixtures of suitable heterocyclic materials which may be used as such i or after suitable'purification, without separation into the individual components.

The hydroxylated diamides previously described and employed as reactants, vary from viscous to sub-resinous or resinous substances, usually dark amber in color.

They show no" solubility in water, or at the most, only a slight Also suitable as react tendency towards solubility. This is due primarily to the fact that the amino nitrogen atom is not basic and no attempt is made to introduce sufficient alkylene oxide and radicals to give solubility, due to such hydrophile group. The reactions involved between the hydroxylated diapropos:

amide's' and:a hydrohalideiof: thef-pyridine series? may be: -illustratedgin the iollowingrmanner I NooRcoi 7 R, momggggg i iger The procedure involved in carrying out theabove indicated reactionsis entirely comparable to,- andoperating conditions; are: the same, as,: in the-manufacture.of-ithe monopyridiniumrcomepounds. described 111413119. various. aforementionedpatents.- The reactions are generallymonducted inn-the presence: of an excessmfvpyridine or the pyridineibase. When there-is an=excessofsuch loaseepresent, the boiling point of-the mixture mericiacidnwithfl pound'imoles of; diethanolamine.

DIPYRIDINIUMCOMROUND i Example 4 v 7 The *same procedure is employed as 'inth mediat'e'ly precedihg' Example-3,-' except that one uses the thydroxylatedgdiamide describedsiunderr the heading Hydroxylated Diamide, Example '7 in combination with a pyridine hydrochloride and pyridine.

DIPYRIDINIUM COMPOUND Emample.-.5

Thesame procedure is followed as "inrtheffour previous; examples exceptth'at instead-of using moreorilessdetermines the reaction temperaturea. 40 pyridine-and pyridinihydrochmride, one lemploysc Time of reactionsis comparatively short, two or three hours being sufficient, if there isv an. excess of.- pyridine or the. pyridine base. The reaction mixture is: preferably stirred constantly; during;

instead: an equivalent amount of the hydrochlo ride of a fraction ofrpy-ridine;base which fraction is characterized by the fact that distils up to 140 C. and 90% distilsup' to 160 C. and the reaction, and at the end of the period of-reaction; fiproductis completelylwatfirrsolublefi VThisfisame the excess of pyridine, or, pyridine base A isidistilled off, along with-any remainingamount-of water, If desired ithe convenient proceduresis.- to useai-hot condenser, i.ie.,- a condenser soreguez latedminaregard to temperature; that water of; reaction; is eliminated, but that. vthe pyridineorr higher boiling pyridine base isreturned .toethemixture...

DIPYRIDINIUM COMPOUND V V Eivample 1 One :ipound mole of :the hydroxylatedrdiamide described under :the heading; fHydroxylated ;Dia:- I mide,. Example 1 or .-Hydroxy1ated Diamide Exe -and leveling agents in thesl aundry, textile, and

dyeing industries; as wetting agents and detergents, rin-i-the caeidewashing of .zfruit, in the; acid! washingmf building stoneyand brick-;. road ;buil'd-. ing and the like; as a constituent ofizsoldering; :fiux preparations; as a flotation reagent in the flotation separation of various -'minerals for flocculation and coagulationofvarious aqueous coal washing waste water, and various trade wastes, and; !the :like; as #germicids; insecticides,- emulsiamplei2,-, is mixed'withfitpoundmoles of pyridine? meiiers fo' rcosmetics,- sp'r-ay oil's, water repellent hydrochloride and" 1 pound :mole of :pyridine for? approximately 2 to 3 hours-at-approximately 150 C.,'. usingtazhot condenser so as J toreflux the pyridine, but permittingjwaterto escape; The reactiontmassr-is stirred: constantly duringrireaction. ossions; and-* more specifically? emulsi At the end .of the period of reaction, the excess; of ipyridine-andlany water present is. removed by vacuum distillation, using only a moderate-:,-vacuumuand approximately 30-40 mm-.- of mercury.-

The resultant product is a; dark red SOIidIO pas y as "a break inducer in doctor treatment of the kind;

sugary mass, and iscompletely; soluble "in- Water.

DIPYRIDINIUM COMPOUND Example 2 textilefinishetc: These-uses-are= by np means exhaustive as *far as industrial application goes; although the most important use'of our new ma terial isas-a dmulsifir for-water-in--oil-'einulvor 'brine in crude petroleum." 7

We -3h'ave found that *the"chemical' compounds hereindescribed which are particularly desir able for 'use as demulsifiers; may also be used! intended to "sweeten. gasoline (See U. S. Patent No:=2;157,223; dated May 9,- 1939, to Sutton.)

Chemical compounds of the kind hereinde--- scribed-:iaresalso: of ;'value=-as surface: tension de- The; same: procedure is employed,lexceptthat: z-pressants: irrzthea acidizationeof: calcareousii-oil-w ons of water bearing strata by means of strong mineral acid, such as hydrochloric acid. Similarly, some members are effective as surface tension depressants or wetting agents in the flooding of exhausted oil-bearing strata.

As to using compounds of the kind herein described as flooding agents for recovering oil from subterranean strata, reference is made to the procedure described in detail in U. S. Patent No. 2,226, 19, dated December 24, 940, to De Groote and Keiser. As to using compounds of the kind herein described as demulsifiers, or in particular as surface tension depressants, in combination with mineral acid for acidization of oil-bearing strata, reference is made to U. S. Patent No. 2,233,383, dated February 24, 1941, to De Groote and Keiser.

The new compounds herein described are of utility, not only for the purposes specifically enumerated in detail, but they also find application in various other industries, processes, and for various uses where wetting agents of the conventional type are used. As to some of such additional uses which are well known, see The Expanding Application of Wetting Agents, Chemical Industries, volume 48, page-324, (1941).

Another use for the compounds herein contemplated is in the prevention of landslides, as described in U. S. Patent No. 2,348,458, dated May 9, 1944, to Endersby.

It may be well to note that polymerization of polyene acids is not limited to the esters, but that the acids per se may be polymerized. This fact is noted, for example, in the aforementioned Johnston Patent No. 2,347,562.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

A dipyridinium compound. selected from the class consisting of CQHaNE F Z ZHA CzHrOH OHSG 0 oiHll iz P N-C2H40-O C RC 0- O CzHrN Py 5 NC2H4 OCOHZ! in which OCRCO is the acid radical of ((IJH2)7ICOH REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,094,609 Kritchevsky Oct. 5, 1937 2,146,408 Shipp Feb. 7, 1939 2,310,873 Sauer Feb. 9, 1943 2,335,262 De Groote Nov. 30, 1943 2,347,562 Johnston Apr. 25, 1944 2,363,504 De Groote Nov. 28, 1944 2,381,115 De Groote Aug. 7, 1945 

